Preparing soluble oils



Patented Apr. 27, 1926.

unirao STATES ,earanr OFFICE;

DE RALPH FRIZELL, OF LOS AN GELES, AND BERT ALLEN STAGNER, OF BERKELEY,

CALIFORNIA, ASSIGNORS 'IO UNION OIL COMPANY OF CALIFORNIA, OF LOS AN- GELES, CALIFORNIA, A CORPORATION- OF CALIFORNIA.

PREPARING SOLUBLE OILS.

No Drawing.

T 0 all whom it may concern:

Be it known that we, DE RALPH FRIZELL and BERT ALLEN STAGNER, citizens of the United States, and residents, respectively, of Los Angeles, in the county of Los Angeles and State of California, and of Berkeley, in the county of Alameda and State of California, have invented certain new and useful Improvements in Preparing Soluble Oils, of which the following is a specification.

Our invention relates to making soluble oils or emulsifiers, such being oils or oil compounds capable of ready dispersion in cold water with slight agitation, whereby a stable emulsion is formed.

One of the principal objects of our invention is the use of waste products from refining crude petroleum, the same being the naphthenic acids or their soaps, of which the sodium naphthenates are especially preferred. v

Naphthenic acids may be obtained from the waste alkali washes in petroleum refineries, being contained in the same as partly saponified products, in a number of ways, such as are described in the copending ap plications of L. L. Rebber, Serial Number 559,612 filed May 9th, 1922, and De R. Frizell, Serial Number 559,614 filed May 9th, 1922.

They are oxidation products of the naphthene series C I-I which are naturally present in petroleum distillates or are formed by the oxidizing action of the sulphuric acid used inpurifying petroleum products or by other oxidizing agents, and consist of a hydrocarbon radical, or a substituted hydrocarbon radical, in combination with a carboxyl group of which hexahydrobenzoic acid, G H COOH, may be taken as illustrative.

In the refining of petroleum distillates, the distillates are treated with sulphuric acid and the acid sludge, containing the sulphonic acids and sulphonates, are drawn 011', naphthenicacids being formed at the same time and remainjn the distillate. The

distillate is then treated with an alkali, such as the alkali metal hydroxides, preferably sodium hydroxide, and the alkali sludge containing the naphthenic acids and naphthenates is drawn ofl.

Application filed. April 1, 1922. Serial No. 548,847.

The naphthenic acids. and naphthenates are present in the waste alkali in a partly saponified condition, and in order to recover them therefrom, we preferably treat the waste alkali with sulphuric or other suitable acid, whereupon the naphthenates are broken up into naphthenic acids and together with the naphthenic acids previously present are thrown out of solution and recovered in any suitable manner.

Saponification is effected by treating with strong sodium hydroxide, added in small amounts to avoid excess, and the sodium naphthenic soaps so formed are then heated and stirred to drive off excess moisture and further mixed with cresol in the proportion of about one part cresol to four parts of the sodium naphthenates by volume, but we do not hereby limit ourselves to the above proportions inasmuch as we have found other proportions to be equally valuable, the above mentioned proportions being merely illustrative.

The resulting product is mixed in varying proportions with mineral oils to form a soluble oil, the proportions varying with the mineral oil taken for a specific use and we find we can use alight oil, such as kerosene, or a heavy oil such as a crude oil, with equally good results for any particular class of Work.

The soluble oils thus produced, With slight agitation are readily emulsified in water, forming stable emulsions, being miscible therein in any proportion.

The emulsions are used in the treatmentv 'of wools, sprays for fruit trees, sheep dips,

er than that made fro] 1 oils made from part mineral and part vegetable or animal origin, and we prefera bly make our soluble oils with the sodium naphthenates obtained from a particular stock and a distillate prepared from that stock, or a similar stock. I However, in either case, the use of cresol with naphthenates increases the stability of emulsions, in comparison to their stability when prepared by other methods, and we may use cresol, the acids of cresol or their salts.

Cresol is generally obtained from coal or wood tar and has the formi1laCH .C H .OH, thus being an' aromatic hydroxyl derivative which has valuable antiseptic properties which make our product especially Valuable for the production of thread cutting emulsion. However, the function of cresol in our invention. is that of a common sol-' vent for the oil and the naphthenic soap whereby emulslons can be made with water wlnch are rendered relatively more permanently stable, its antiseptic qualities being purely incidental to its use in the process described.

Commercial cresol contains three isomeric orms and according to one authority (Lunge, Coal Tar and Ammonia, Vol. II, pp. 772) has the following constitution:

. Per cent.

Iso cresols 95 Phenol 2 Xylenols 1 Higher phenols, pyridene bases, residues,

water, etc 2 In View of this content of aromatic hydroxyl derivatives, the term cresol where used in' the claims is intended to include all equivalents of cresol or contained derivatives.

The emulsions made from our soluble oi-ls easily pass all Government tests which require that polished brass or copper must not turn green after standing. in' an emulsion twenty-four hours, and that polished steel must not be corroded after standing in an sodium naphthenates with cresol and dissolving the resulting compound in an oil.

4. The process of preparing soluble oils which consists in saponifying naphthenic acids with sodium hydroxide, mixing the sodium 'naphthenates with cresol and dissolving the resulting compound in a mineral-oil.

5. The process of preparing soluble oils which consists in saponifying*naphthenic acids, with sodium hydroxide and adding about one part of cresol to about four parts by volume of the resulting naphthenic soaps then dissolving the resulting compound in a mineral oil.

6. The method of n'iaking an emulsion from hydrocarbon oils which consists in mixing sodium naphtlienic soaps with cresol dissolving the mixture in the aforesald 011s and dispersing the resulting compound in water.

7. The method of making an emulsion from hydrocarbon oils, which consists in mixing sodium naphthenic soaps with cresol inthe proportion of about one part of cresol to about four parts by volume of sodium naphthenic soaps, dissolving the mixture in the hydrocarbon oil then dispersing the resulting compound in water.

8; A soluble oil comprising an alkali metal naphthenate, cresol and oil.

9. A. soluble oil comprising naphthenate, cresol and an oil.

10. A soluble oil comprising sodimn naphthenate, cresol and a mineral oil.

11. A soluble oil comprising about one part of cresol to four parts by volume of sodium naphthenate, and a mineral oil.

12. An emulsion comprising sodium sodium naphthenate, cresol, mineral oil and water.- comprising cresol,-

13. An emulsion sodium naphthenate, a mineral oil and water; the cresol being in the proportion ,of

about one part of cresol to four parts of sodium naphthenate by volume.

Signed at Los'lngeles, in the county of Los Angeles, and State of California, this 27th day of March 1922.

DE RALPH FRIZELL.

Signed at Oleum, in the county of Contra Costa, and State of California, this 25th day of March, 1922.

, BERT ALLEN STAGNER. 

